Compositions of matter and methods and steps of making and using the same



United States Patent COMPOSITIONS OF MATTER AND METHODS AND STEPS OFMAKING AND USING THE SAME Mortimer T. Harvey, South Orange, and Peter L.Rosamilia, Newark, N. J., assignors to Harvel Research Corporation, acorporation of New Jersey No Drawing. Original application February 17,1951, Serial No. 211,576. Divided and this application June 9, 1954,Serial No. 435,621

3 Claims. (Cl. 260--45.5)

The present invention relates to the treatment and to the treatmentproducts of residues obtained by the furfural extractive distillationmethod for purification of butadiene which residues are considered to befor the most part due to a reaction of butadiene with furfuraldehyde.From these residues a compound has been isolated and shown to be2,3,4,5-bis (n -butenylene)-tetrahydrofurfural. A report on the subjecthas been made by Swadesh, Leslie and Dunlap in Industrial andEngineering Chemistry, vol. 40, pp. 2216 to 2220, November 1948, towhich report reference is hereby made.

The present invention relates more particularly to reaction products ofsaid residues by (1) treatment with heat and katenoid condensing orpolymerizing agents and (2) reactions with other compounds. And thepresent invention further relates to methods and steps of obtaining theproducts of the present invention and to physical combinations of theproducts of the present invention with other materials.

Illustrative examples of the methods and products of the presentinvention are given below, all parts being given by weight unlessotherwise indicated.

Examples of agents used in the practice of the present invention for thetreatment of the starting materials and herein called katenoidcondensing agents are sulphuric acid, monoalkyl sulphates, dialkylsulphates, e. g. monomethyl, monoethyl, monopropyl sulphates and highermonoalkyl sulphates and dialkyl sulphates, e. g. dimethyl, diethyl,dipropyl sulphates and higher dialkyl sulphates, also other knownequipment hydrocarbon sulphates, hydrochloric acid and phosphoric acidand hydrocarbon equivalents of these and other known equivalentsincluding maleic acid which also can be used as a condensing agent butin this case the maleic acid itself may enter into the reaction to formpart of the condensation product.

We have found that the residues that are used as starting materials inthe practice of the present invention have the following reactionproperties and give the following treatment products.

The properties of the residue starting materials are as follows forresidue from Phillips Petroleum Companys plant at Bartesville, Oklahoma:

Although the residue starting materials contain several products, forsome purposes it is considered to have a molecular weight of 192 whichis the molecular weight of di-butadiene monofurfuraldehyde copolymer.

Polymerizations: 100 grams of residue starting materials In the examplesbelow the residue starting materials are treated in terms as thoughthese materials were all di-butadienemonofurfural copolymers but this ismerely for use as an arbitrary guide for manufacturing purposes.

Example A 200 parts (16%. water) residue starting material, 100 partsacetone, 1 part NaOH and 3 parts water were refluxed for one-half hour.The yield of dehydrated product was 190 grams, the product hereinafterbeing known as product A. The reaction was exothermic and this togetherwith an increase in yield over a theoretical yield tends to indicate.the presence of an aldehyde.

Example B 100 parts of residue starting material which has been heatedto 125 C. to remove water and other volatiles and 10 parts of VYNS (acopolymer of about vinyl chloride, and 10% vinyl acetate) were heated to150? C. giving a soft rubbery gel-like product hereinafter known asproduct B andhaving a high V. M. and P. naphtha and toluol resistance.

Example C parts of product A and 10 parts VYNS (a copolymer of about 90%vinyl chloride and 10% vinyl acetate) were heated to 150 C. giving asoft rubbery gel-like product hereinafter known as pro-duct C and havinga high V. M. and P. naphtha and toluol resistance.

Example D 100 parts of residue starting material which has been heatedto C. to remove water and other volatiles, 1 part NaOH in 3 parts ofwater and 10 parts of sulfur were heated to C. Then there was addedthereto 10 parts VYNS (copolymer of about 90% vinyl chloride and 10%vinyl acetate) to give a hard product hereinafter known as product D.

The following examples are given merely as illustrations of reactionswith katenoid condensing agents or catalysts, such as acid and alkalinecatalysts.

Example E 100 parts of residue starting material which has been heatedto 125 C. to remove water and other volatiles, and 3 parts of diethylsulphate were heated to from 100 C. to about 125 C. until a brittlegrindable but still fusible mass is obtained and is known hereinafter asproduct E.

Example F 100 parts of dehydrated residue starting material as inExample B, 3 parts of diethyl sulfate and 2 parts of paraformaldehydewere heated carefully to about 100 C. to about 125 C. to obtain abrittle but still fusible mass hereinafter known as product F. Thisproduct F has a lower volatility at 260 C. and a lower content ofsolvent extractable material than product E, using toluene or V. M. andP. naphtha as the solvent.

Example G 100 parts of dehydrated residue starting material as inExample B and parts of maleic acid (anhydride) were heated carefully toabout 100 C. to about 125 C. to obtain a brittle but still fusible masshereinafter known as product G.

Example H 100 parts of residue starting material which has beendehvdrated bv heating to 125 C. is heated with 10 parts of maleicanhvdride at temperatures upward from about 100 C.-120 C. until there isobtained a brittle fus ble mass, which can be around into a powder andused in the same manner as Example E above. This product is kn nhereinafter as product H. he additi n of h a methvlene tetramine or hexmethvlene tetram neime sne ds no the cure considerablv to i e heathardness which is an advantage in quick molding.

Example I 100 narts of the residue starting material as used in ExamnleR above and s o rts of diethvl l hate are he ted t fr m about 100 C. toabout 17 C. to obtain a thick n d liquid or vi c s ma s. This pr d ct,kn wn he in f er as pr duct I in ermediate. can be further hea ed l neor with an aldehvde p du t such as p raformaldehvde (about 5 nartsl toreach further sta es of thickening and can he finallv set to a infnsihleb y. This nroduct can he used for imore natin fabrics or f r making lamti ns of w od. o ner, f brics or other pr ducts. The nroduct also can beused alone or with rubber or oh nolic resins as a binder fo a be to ndother m t rials in brake l nin s. Also it can be cured, for examnle. a but C. for about 16 hours to obtain an infusible b dv. This latter can bepulverized and used as a fricti n fortifier in brake linings and clutchfarin s and is ident fied as product I. cured.

The residue starting materials can be inc rporated directly bv heat orhv heat and an a id or alkaline catalyst into cashew nut shell l ouid(CNQL) and its derivatives such as oolvmerized CNSL. d st llates of CNSLsuch as cardol. distillate residues of CNSL and the polymerized residuesof CNSL.

Example I 120 arts of CNSL distillation residue. 40 parts of dehydratedresidue starting material identified above, 8 parts of diethvl sulohateand 5 parts of paraformaldehyde are heated together at 100 C. until aviscous intermediate product is formed. This intermediate product, knownhereinafter as product I intermediate. can be mixed into asbestos andother fillers in the making of brake linings and clutch facings and canbe incorporated into rubber to increase oil resistance. And thisintermediate product can be further cured, for example, at about 150 C.for 16 hours to obtain an infusible mass which can be pulverized. Thepulverized product, for example, at 20 to 40 mesh, can be used forfriction fortifying material in brake linings and clutch facings.

The products E, F, G, H, I and J, singly or in mixtures of two or moremay be ground to a fine powder and used as a brake lining binder aloneor with hexamethylene tetramine and lime. They may be used with phenolaldehyde resins for further heating to an infusible mass. Each and allof these compounds, including each of the products A to I can be used asfriction fortifying material.

Example K 100 parts of residue starting material after dehydration at125 C., 4 parts of a solution of 1 part of caustic soda in 3 parts ofwater and 10 parts of sulphur are heated together at about 125 C. toabout 150 C. to incorporate the sulphur into the residue startingmaterial.

The soft rubbery gel-like reaction products obtained in Examples B and Cabove by combining the residue starting materials with VYNS, can beincorporated into Buna-N (GR-A) polymers, GR-S polymers, neoprene andnatural rubber for improving oil resistance and for obtaining a verysoft stock which is useful in printing rolls.

The residue starting material and the intermediates of the examplesabove can be hydrogenated to make variations of the examples above.

Example L 200 parts of the residue starting materials identified aboveand containing about 16% water were distilled at about 40 millimeters ofmercury pressure. Up to 175 C. 45 parts came over as a distillate ofwhich 32 parts were water and 13 parts were an oily liquid heavier thanwater. Between 175 C. and 240 C. about parts more came over as adistillate, with some cracking at the end. This left a residue which wasa solid, pulverizable mass.

A friction fortifying material can be made by placing a quantity of theresidue starting material in a kettle having a stirrer and heating up toabout 300 C. with stirring until about 50% of the starting material hascome out as distillate. The residue will be a hard, friable, infusiblematerial which will be pulverized by the stirrer. This pulverizedmaterial can be used as a friction fortifier when added to brake liningand clutch facing mixtures well known in the art, including rubber,asbestos, coal, coke and other materials.

The distillate can be treated as in Examples A to J above to makevariations of those examples.

Example M parts of Buna-N (GR-A), 5 parts of zinc oxide, 100 parts ofproduct B (or product C), 5 parts of stearic acid, 1.5 parts sulphur and1.5 parts Altax (accelerator) are milled together on a rubber mill. Thiscomposition can be cured for 30 minutes at about C. to give a soft,resilient compound suitable for making into printing rolls. The Shorehardness is about 37 to 42.

This application is a division of our copending application Serial No.211,576, filed February 17, 1951, now abandoned.

Having thus described our invention, what we claim 1. The method forsulfurizing residue obtained from the furfural extractive distillationmethod for the purification of butadiene and containingbutadient-furfural reaction product comprising heating together saidresidue and sulfur in the presence of a caustic alkali as a catalyst.

2. The product of the process of claim 1.

3. A novel composition of matter produced by heat combining (A)copolymer of vinyl chloride and vinyl acetate and (B) a sulfurizedresidue, said sulfurized residue before being sulfurized being obtainedas a residue from the furfural extractive distillation method for thepurification of butadiene and containing butadiene-furfural reactionproduct, the quantity of (B) being greater than the quantity of (A).

References Cited in the file of this patent UNITED STATES PATENTS2,483,903 Herbolsheimer Oct. 4, 1949

1. THE METHOD FOR SULFURIZING RESIDUE OBTAINED FROM THE FURFURALEXTRACTIVE DISTILLATION METHOD FOR THE PURIFICATION OF BUTADIENE ANDCONTAINING BUTADIENT-FURFURAL REACTION PRODUCT COMPRISING HEATINGTOGETHER SAID RESIDUE AND SULFUR IN THE PRESENCE OF A CAUSTIC ALKALI ASA CATALYST.